Uranium hexamethoxide and mixed methoxyuranium(VI) fluorides: Facile syntheses from UF6 and a nuclear magnetic resonance investigation of structure and chemical dynamics

Edward A. Cuellar, Tobin J Marks

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29 Citations (Scopus)

Abstract

Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.

Original languageEnglish
Pages (from-to)2129-2137
Number of pages9
JournalInorganic Chemistry
Volume20
Issue number7
Publication statusPublished - 1981

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Uranium
Fluorides
uranium
fluorides
Charge transfer
charge transfer
Nuclear magnetic resonance
Ligands
nuclear magnetic resonance
ligands
Chemical shift
synthesis
electronic spectra
Stoichiometry
chemical equilibrium
stoichiometry
Substitution reactions
Metals
substitutes
temperature dependence

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Uranium hexamethoxide and mixed methoxyuranium(VI) fluorides: Facile syntheses from UF6 and a nuclear magnetic resonance investigation of structure and chemical dynamics",
abstract = "Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.",
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T1 - Uranium hexamethoxide and mixed methoxyuranium(VI) fluorides

T2 - Facile syntheses from UF6 and a nuclear magnetic resonance investigation of structure and chemical dynamics

AU - Cuellar, Edward A.

AU - Marks, Tobin J

PY - 1981

Y1 - 1981

N2 - Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.

AB - Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.

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